JP3726609B2 - Stain-resistant glossy decorative board - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to a diallyl phthalate-based stain-resistant decorative veneer that can be easily wiped off with a dry cloth, paper or the like even when soiling due to oil-based magic ink or the like adheres.
[0002]
[Prior art]
Conventionally, diallyl phthalate-based resin decorative boards are known as thermosetting resin decorative boards having weather resistance, natural texture, heat resistance, chemical resistance, and dimensional stability. Conventionally, diallyl phthalate-based resin decorative boards have 90-93% by weight diallyl phthalate prepolymer, 7-10% by weight diallyl phthalate monomer, and are resin-dissolved containing curing agent, mold release agent, polymerization preparation agent, filler, UV absorber. Printed decorative paper is immersed in a solution or a resin solution containing 30 to 90% by weight of diallyl phthalate prepolymer and 10 to 70% by weight of unsaturated polyester in a curing agent, mold release agent, polymerization preparation agent, filler, and UV absorber. Alternatively, a decorative board is obtained by hot-pressing a coated impregnated coated decorative paper with a base material.
[0003]
In addition, as shown in Japanese Patent Publication Nos. 6-24808 and 6-24809 and JP-A-3-255138, other resins are added to the diallyl phthalate resin to improve the properties as a decorative board. ing. However, such a decorative board does not have a characteristic that can wipe off dirt such as oil-based magic ink.
[0004]
As a method for producing a stain-resistant decorative board, for example, a method for applying a paint having excellent water repellency and oil repellency on a decorative board as disclosed in JP-A-10-428 has been proposed. In the method, a coating process is further added on top of the conventional production processes such as impregnation and hot-press molding, so that the production cost is remarkably increased.
[0005]
Japanese Patent Application Laid-Open No. 1-249747 proposes a method for producing a stain-resistant decorative board using fluorine-containing diallyl isophthalate as a raw material. However, the raw material itself is expensive, and the cost becomes high.
[0006]
[Problems to be solved by the invention]
As described above, the production of a stain-resistant decorative board has the disadvantage that the production cost is significantly higher than that of a conventional decorative board. Further, most of these stain-resistant decorative boards are not glossy. The present invention is intended to solve such problems.
[0007]
[Means and Actions for Solving the Problems]
The present invention solves the above problems, to veneer diallyl phthalate-based thermosetting resin composition 100 parts by weight, RSiO _3/2 units and the organopolysiloxane that having a acryloxy group or methacryloxy group / Or R ′ ₂ SiO _2/2 units (R and R ′ represent a lower alkyl group or a lower alkoxy group), and a part of the lower alkyl group is — (CH ₂ ) _n R ″ (R ″ is represents an acryloxy group or methacryloxy radical, n is 1-3.) to consist of curing agent in O organopolysiloxane 3-50 parts by weight and the thermosetting resin of the two-dimensional structure or three-dimensional structure substituted with A stain-resistant glossy decorative board for oil-based magic ink or the like, which is obtained by laminating an impregnated paper cloth impregnated in an impregnated base material on a decorative board base material and hot-press molding.
[0008]
The diallyl phthalate-based thermosetting resin composition for a decorative board includes diallyl phthalate prepolymer alone, 90 to 93 parts by weight of the prepolymer, 7 to 10 parts by weight of diallyl phthalate monomer, and 30 to 90 parts by weight of the prepolymer. It consists of 10 to 70 parts by weight of saturated polyester, 80 to 90 parts by weight of unsaturated polyester and 10 to 20 parts by weight of diallyl phthalate monomer.
[0009]
The diallyl phthalate prepolymer referred to in the present invention is a diallyl orthophthalate prepolymer, diallyl isophthalate prepolymer, diallyl terephthalate prepolymer alone or a copolymer thereof or a mixture thereof.
[0010]
The unsaturated polyester may be a normal liquid or solid unsaturated polyester resin, for example, a polybasic unsaturated acid such as maleic acid, fumaric acid, itaconic acid, phthalic acid, adipic acid or a mixture with a saturated acid. Reaction product of polyhydric alcohol such as ethylene glycol, propylene glycol, diethylene glycol, hydrogenated bisphenol A, or air-curable unsaturated polyester resin, for example, in addition to the above acid components, tetrahydrophthalic acid, 3,6-endo As the alcohol component, an acid containing an aliphatic cyclic unsaturated acid such as methylenetetraphthalic acid or methyl-3,6-endomethylenetetraphthalic acid, or a polyester resin produced from allyl glycidyl ether is suitable.
[0011]
Examples of the curing agent referred to in the present invention include peroxide curing agents such as benzoyl peroxide, tertiary butyl perbenzoate, methyl ethyl ketone peroxide, and dicumyl peroxide.
[0012]
In addition to the curing agent, various reactive monomers and additives commonly used in the technical field, such as internal mold release agents, fillers, flame retardants, polymerization preparation agents, ultraviolet absorbers, pigments, etc., are added as necessary. can do.
[0013]
Examples of the impregnated substrate include printing paper (printing pattern paper), kraft paper, non-woven fabric, woven fabric, and the like. In order to produce an impregnated paper cloth using the composition of the present invention, the resin composition of the present invention is dissolved in an appropriate solvent, for example, an organic solvent such as acetone, toluene, methyl ethyl ketone and the impregnated base material is impregnated with an appropriate amount. After drying, it can be pre-cured as necessary. The impregnated resin adhesion amount may be 80 to 250 g / cm ² .
[0014]
Acryloxy The organopolysiloxane that have a group or methacryloxy group used in the present invention, the _{RSiO 3/2} units and / or _{R '2 SiO 2/2} units (R and R' is a lower alkyl group or a lower alkoxy group An organopolysiloxane in which a part of the lower alkyl group is substituted with — (CH ₂ ) _n R ″ (where R ″ represents an acryloxy group or a methacryloxy group, and n is 1 to 3). It is.
[0015]
Examples of the organopolysiloxane in the present invention include γ-methacryloxypropylmethyldimethoxysilane (hereinafter referred to as silane A), γ-methacryloxypropyltrimethoxysilane (hereinafter referred to as silane B), and γ-acryloxypropyltrimethoxysilane (hereinafter referred to as silane A). Any one of 0.05 to 0.30 mol% of silane C) is reacted with 0 to 0.95 mol% of dimethyldiethoxysilane (hereinafter referred to as silane D), methyltriethoxysilane (hereinafter referred to as silane E) or the like. Can be obtained.
[0016]
The reaction may be carried out in an aqueous solution at 60 ° C. for 5 hours in the presence of an acid catalyst. After completion of the reaction, washing with water and toluene is sufficient to completely remove the solvent in vacuum.
[0017]
When silane A and silane D are reacted, an organopolysiloxane having a two-dimensional structure is obtained. When silane B, silane D, and silane E are combined, an organopolysiloxane having a three-dimensional structure is obtained.
[0018]
The blend of the resin composition in the present invention is 0 to 100 parts by weight of diallyl phthalate prepolymer, 0 to 100% by weight of unsaturated polyester, and 100 parts by weight of mixed resin of diallyl phthalate monomer 0 to 20% by weight, based on acryloxy group or methacryloxy group. that having a at the addition amount of the organopolysiloxane is from 3 to 50 parts by weight, the amount of the organopolysiloxane that the plane of the cost into account preferably have a acryloxy group or methacryloxy group is 5 to 30 parts by weight The range is appropriate.
[0019]
If the amount is less than 3 parts by weight, a decorative plate excellent in stain resistance on the surface of the decorative plate, which is the object of the present invention, cannot be obtained. If the amount exceeds 50 parts by weight, the decorative plate surface is brushed and a decorative plate having high glossiness is obtained. Absent.
[0020]
The resin-impregnated paper cloth of the present invention is laminated and pressure-molded on plywood, particle board, medium density fiber board (MDF), inorganic board, and kraft paper impregnated with resin, which are base materials for decorative boards. It becomes. Molding is performed for 1 to 15 minutes, a pressure of 10 to 25 kg / cm ² , a temperature of 120 to 190 ° C., and a fully cured decorative board at a low pressure. The decorative plate includes a laminated decorative plate. Next, the present invention will be described in detail by way of examples and comparative examples. The part of an Example and a comparative example shows a weight part.
[0021]
[Examples and comparative examples]
Example 1
Diallyl orthophthalate prepolymer (methyl ethyl ketone 50 wt% solution viscosity (30 ° C.) 96.5 cp, iodine value 56.7, manufactured by Daiso Corp.) 80 parts, fumaric acid 10 mol / ethylene glycol 3 mol / propylene glycol 6 mol / unsaturated polyester 20 parts of acid value 15 in hydrogenated bisphenol A1 molar composition, silane B 0.1 mol, silane D 0.5 mol, is that the organopolysiloxane obtained from silane E 0.4 mol (number average molecular weight 7500) 5 parts, 4 parts of benzoyl peroxide, 0.4 parts of internal mold release agent (Zelec UN, manufactured by DuPont), 0.03 part of hydroquinone (polymerization preparation agent), fine powder silica (Carplex, Shionogi & Co., Ltd.) 4) Dissolve 4 parts in acetone and toluene to prepare a resin solution, and impregnate 80 g / cm ² of printed pattern paper. 180 g / cm ² of impregnated paper was obtained.
[0022]
The impregnated paper was placed on a 16 mm particle board, and a decorative board was obtained by hot press molding at 130 ° C., 15 kg / cm ² for 12 minutes. The obtained decorative board passed the water resistance, weather resistance, chemical resistance, etc. stipulated in JISK6902, K5400 and JAS, and the gloss measured with a gloss meter (Gs20) was 90-91, and oily magic ink was wiped off. It was possible to wipe twice in a test (drawing 5 cm using a 15 mm oil-based magic ink pen and wiping with a dry cloth. This was repeated three times at the same place).
[0023]
Example 2
Except that in Example 1 Odor Te was the amount of the organopolysiloxane to 10 parts to obtain a decorative plate in the same manner as in Example 1. The obtained decorative board had a gloss of 88 to 89, and it could be wiped at once in the oil-based magic ink wiping test as compared to Example 1, and passed various tests.
[0024]
Example 3
Except that in Example 1 Odor Te was the amount of the organopolysiloxane to 30 parts to obtain a decorative plate in the same manner as in Example 1. The obtained decorative board has a gloss of 80 to 82, and can be wiped at once in the oil-based magic ink wiping test as compared to Example 1, and passed various tests.
[0025]
Example 4
90 parts of diallyl phthalate prepolymer, 10 parts of the same organopolysiloxane as in Example 1, 4 parts of benzoyl peroxide, 0.4 part of internal mold release agent, 0.03 part of hydroquinone, and 4 parts of finely divided silica are added with acetone and toluene. A decorative board was obtained in the same manner as in Example 1 except that the resin solution was prepared by dissolving the resin. The obtained decorative board had a gloss of 83 to 85, and passed the various tests including the oil-based magic ink wiping test in the same manner as in Example 1.
[0026]
Example 5
90 parts of diallyl phthalate prepolymer, 10 parts of diallyl phthalate monomer, 10 parts of the same organopolysiloxane as in Example 1, 4 parts of benzoyl peroxide, 0.4 part of internal mold release agent, 0.03 part of hydroquinone, fine powder silica A decorative board was obtained in the same manner as in Example 1 except that 4 parts were dissolved in acetone and toluene to prepare a resin solution. The obtained decorative board had a gloss of 87 to 88 and passed various tests including the oil-based magic ink wiping test in the same manner as in Example 1.
[0027]
Example 6
90 parts of unsaturated polyester, 10 parts of diallyl orthophthalate monomer, 5 parts of the same organopolysiloxane as in Example 1, 4 parts of benzoyl peroxide, 0.4 part of internal mold release agent, 0.03 part of hydroquinone, fine powder silica 4 A decorative board was obtained in the same manner as in Example 1 except that the resin solution was prepared by dissolving the part in acetone and toluene. The obtained decorative board had a gloss of 75 to 78 and passed various tests including the oil-based magic ink wiping test in the same manner as in Example 1.
[0028]
Example 7
Silane B 0.3 mol, to obtain silane D 0.4 mol, silane E is that the organopolysiloxane obtained from 0.3 mol (number average molecular weight 5800) except for using the veneer in the same manner as in Example 1 . The obtained decorative board had a gloss of 86 to 88 and passed various tests including the oil-based magic ink wiping test in the same manner as in Example 1.
[0029]
Example 8
Silane B 0.1 mol, to obtain silane D 0.8 moles, except using silane E is that the organopolysiloxane obtained from 0.1 mol (number-average molecular weight 11000) is a decorative plate in the same manner as in Example 1 . The obtained decorative board had a gloss of 87 to 88 and passed various tests including the oil-based magic ink wiping test in the same manner as in Example 1.
[0030]
Example 9
Silane B 0.1 mol, to obtain silane D 0.2 mol, except using silane E is that the organopolysiloxane obtained from 0.7 mol (number average molecular weight 4200) is a decorative plate in the same manner as in Example 1 . The obtained decorative board had a gloss of 82 to 83 and passed various tests including the oil-based magic ink wiping test in the same manner as in Example 1.
[0031]
Example 10
Silane A 0.2 molar, was except for using silane D is that the organopolysiloxane obtained from 0.8 mol (number average molecular weight 8100) in the same manner as in Example 1 to obtain a decorative board. The obtained decorative board had a gloss of 78-80 and passed various tests including the oil-based magic ink wiping test in the same manner as in Example 1.
[0032]
Example 11
Silane B 0.2 mol and except for using silane E is that the organopolysiloxane obtained from 0.8 mol (number average molecular weight 3600) in the same manner as in Example 1 to obtain a decorative board. The obtained decorative board had a gloss of 81 to 82 and passed various tests including the oil-based magic ink wiping test in the same manner as in Example 1.
[0033]
Example 12
Silane C 0.1 mole, to obtain silane D 0.5 mol, is that the organopolysiloxane obtained from silane E 0.4 mol (number average molecular weight 7600) except for using the veneer in the same manner as in Example 1 . The obtained decorative board had a gloss of 88 to 89 and passed various tests including the oil-based magic ink wiping test in the same manner as in Example 1.
[0034]
Comparative Example 1
80 parts of diallyl orthophthalate prepolymer, 10 parts of fumaric acid / 3 moles of ethylene glycol / 6 moles of propylene glycol / 1 mole of hydrogenated bisphenol A, 20 parts of unsaturated polyester having an acid value of 15 parts, 4 parts of benzoyl peroxide, internal release A decorative board was obtained in the same manner as in Example 1 except that 0.4 part of the agent, 0.03 part of hydroquinone, and 4 parts of fine powdered silica were dissolved in acetone and toluene to prepare a resin solution. The resulting decorative board has a high glossiness of 92 to 93, but cannot be wiped off with a dry cloth, paper, etc. when dirt due to oil-based magic ink or the like adheres.
[0035]
Comparative Example 2
Except that Example 1 Odor Te but the amount of the organopolysiloxane in 2 parts to obtain a decorative plate in the same manner as in Example 1. The resulting decorative board has a high glossiness of 92 to 93, but cannot be wiped off with a dry cloth, paper, etc. when dirt due to oil-based magic ink or the like adheres.
[0036]
Comparative Example 3
Except that in Example 1 Odor Te was the amount of the organopolysiloxane to 60 parts to obtain a decorative plate in the same manner as in Example 1. The obtained decorative board can be easily wiped off with a dry cloth, paper, etc. even when soiled with oil-based magic ink or the like adheres, but brushing occurs on the surface and the glossiness is reduced to 50 to 55.
[0037]
Comparative Example 4
80 parts of diallyl orthophthalate prepolymer, 10 parts of fumaric acid / 3 moles of ethylene glycol / 6 moles of propylene glycol / 1 mole of bisphenol A hydrogenated, 20 parts of unsaturated polyester having an acid value of 15, silane D 0.5 mole, silane E 10 parts of organopolysiloxane having no functional group obtained from 0.5 mol (number average molecular weight 6800), 4 parts of benzoyl peroxide, 0.4 part of internal mold release agent, 0.03 part of hydroquinone, fine powder silica 4 A decorative board was obtained in the same manner as in Example 1 except that the resin solution was prepared by dissolving the part in acetone and toluene. The obtained decorative board has a whitened surface, and when dirt due to oil-based magic ink or the like adheres, it cannot be wiped off with a dry cloth or paper. Even if a polysiloxane resin having no functional group is added in this way, it does not react with the diallyl orthophthalate prepolymer, so that an oil repellency effect cannot be obtained.
[0038]
【The invention's effect】
As described above, according to the present invention described above, even if dirt due to oil-based magic ink or the like adheres, it can be easily wiped with a dry cloth, paper, etc., and the glossiness of the surface is high, water resistance, weather resistance, A decorative board having excellent chemical properties can be obtained.

Claims (1)

To veneer diallyl phthalate-based thermosetting resin composition 100 parts by weight, and the organopolysiloxane that having a acryloxy group or methacryloxy group _{RSiO 3/2} units and / or _{R '2 SiO 2/2} units ( R and R ′ each represent a lower alkyl group or a lower alkoxy group.) A part of the lower alkyl group represents — (CH ₂ ) _n R ″ (R ″ represents an acryloxy group or a methacryloxy group, and n represents 1 a to 3 a.) 2-dimensional structure or three-dimensional structure of the O organopolysiloxane 3-50 parts by weight and the resin composition is impregnated base material, characterized by comprising the curing agent of the thermosetting resin substituted with A stain-resistant glossy decorative board for oil-based magic ink or the like, which is obtained by laminating an impregnated paper cloth impregnated into a decorative board base material with hot pressing.